Pesticide Residue Fast Screening Using Thermal Desorption Multi-Scheme Chemical Ionization Mass Spectrometry (TD-MION MS) with Selective Chemical Ionization

In this work, the detection characteristics of a large group of common pesticides were investigated using a multi-scheme chemical ionization inlet (MION) with a thermal desorption unit (Karsa Ltd.) connected to an Orbitrap (Velos Pro, Thermo Fisher Scientific) mass spectrometer. Standard pesticide mixtures, fruit extracts, untreated fruit juice, and whole fruit samples were inspected. The pesticide mixtures contained 1 ng of each individual target. Altogether, 115 pesticides were detected, with a set of different reagents (i.e., dibromomethane, acetonylacetone, and water) in different polarity modes. The measurement methodology presented was developed to minimize the common bottlenecks originating from sample pretreatments and nonetheless was able to retrieve 92% of the most common pesticides regularly analyzed with standardized UHPLC-MSMS (ultra-high-performance liquid chromatography with tandem mass spectrometry) procedures. The fraction of detected targets of two standard pesticide mixtures generally quantified by GC-MSMS (gas chromatography with tandem mass spectrometry) methodology was much less, equaling 45 and 34%. The pineapple swabbing experiment led to the detection of fludioxonil and diazinon below their respective maximum residue levels (MRLs), whereas measurements of untreated pineapple juice and other fruit extracts led to retrieval of dimethomorph, dinotefuran, imazalil, azoxystrobin, thiabendazole, fludioxonil, and diazinon, also below their MRL. The potential for mutual detection was investigated by mixing two standard solutions and by spiking an extract of fruit with a pesticide’s solution, and subsequently, individual compounds were simultaneously detected. For a selected subgroup of compounds, the bromide (Br-) chemical ionization characteristics were further inspected using quantum chemical computations to illustrate the structural features leading to their sensitive detection. Importantly, pesticides could be detected in actual extract and fruit samples, which demonstrates the potential of our fast screening method.Peer reviewe

Pre-screening of pesticides using straight radiation chemical ionization and Orbitrap mass spectrometry

Utilization of pesticides in the modern agriculture is often indispensable for gaining good crops. However, pesticides are abundantly being used in too hight quantities which leads to potential health risks for the consumers. Currently there are no pre-screening methods for monitoring the levels of pesticides in food, but only a negligible small percentage of all goods are being tested using the laborious standardized methods. This master’s thesis is an investigation, that was carried out in the wet laboratory of KARSA Oy Ltd, on 10 different pesticides: Glyphosate, Thiabendazole, 2-phenylphenol, Chlorpyrifos, Fludioxonil, Chlormequat, Bupirimate, Diflubenzuron, Fenpyrazamine and 2,4-dichlorophenoxyacetic acid. Pesticides were ionized using straight radiation chemical ionization (SRCI) in positive and negative modes without any added reagent and also using bromide, nitrate, acetonylacetone and acetone as reagents. Charged target molecules and adducts were detected using Thermo fisher Iontrap/Orbitrap (LTQ Orbitrap velos pro upgraded) mass spectrometer. After the initial method development and scoping measurements pesticides were studied both individually and as a mixture of all 10 pesticides. Sample solutions were first injected with syringe so that the solvent and targets evaporated at the same time inside the desorber heating block of SRCI inlet. In these syringe injection measurements, the desorber temperature was set at 150 °C. Mass range at 125–750 has been used for all the pesticides except for Chlormequat (100–750). After the syringe injection measurements, the mixture of 10 pesticides was analysed by TCM filters. Target solutions of 1 µl volume were placed on filters and after the solvents had evaporated the filters were heated from room temperature to 245°C using the same setup as with the syringe injections. In conclusion, with syringe injections 7 pesticides out of 10 were detected using positive and negative mode without any added reagent. The highest target intensities were recorded from TCM filters. Overall, applying the SRCI-Orbitrap setup for pesticide pre-screening from target solutions resulted in the detection of 9 pesticides out of 10

Pesticide Residue Fast Screening Using Thermal Desorption Multi-Scheme Chemical Ionization Mass Spectrometry (TD-MION MS) with Selective Chemical Ionization

In this work, the detection characteristics of a large group of common pesticides were investigated using a multi-scheme chemical ionization inlet (MION) with a thermal desorption unit (Karsa Ltd.) connected to an Orbitrap (Velos Pro, Thermo Fisher Scientific) mass spectrometer. Standard pesticide mixtures, fruit extracts, untreated fruit juice, and whole fruit samples were inspected. The pesticide mixtures contained 1 ng of each individual target. Altogether, 115 pesticides were detected, with a set of different reagents (i.e., dibromomethane, acetonylacetone, and water) in different polarity modes. The measurement methodology presented was developed to minimize the common bottlenecks originating from sample pretreatments and nonetheless was able to retrieve 92% of the most common pesticides regularly analyzed with standardized UHPLC–MSMS (ultra-high-performance liquid chromatography with tandem mass spectrometry) procedures. The fraction of detected targets of two standard pesticide mixtures generally quantified by GC–MSMS (gas chromatography with tandem mass spectrometry) methodology was much less, equaling 45 and 34%. The pineapple swabbing experiment led to the detection of fludioxonil and diazinon below their respective maximum residue levels (MRLs), whereas measurements of untreated pineapple juice and other fruit extracts led to retrieval of dimethomorph, dinotefuran, imazalil, azoxystrobin, thiabendazole, fludioxonil, and diazinon, also below their MRL. The potential for mutual detection was investigated by mixing two standard solutions and by spiking an extract of fruit with a pesticide’s solution, and subsequently, individual compounds were simultaneously detected. For a selected subgroup of compounds, the bromide (Br–) chemical ionization characteristics were further inspected using quantum chemical computations to illustrate the structural features leading to their sensitive detection. Importantly, pesticides could be detected in actual extract and fruit samples, which demonstrates the potential of our fast screening method